CN107233882A - The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application - Google Patents
The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application Download PDFInfo
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- CN107233882A CN107233882A CN201710446994.3A CN201710446994A CN107233882A CN 107233882 A CN107233882 A CN 107233882A CN 201710446994 A CN201710446994 A CN 201710446994A CN 107233882 A CN107233882 A CN 107233882A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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Abstract
The invention discloses a kind of Ru/SnO that burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application.The present invention uses infusion process by RuCl3It is supported on the SnO prepared with ammonia water precipitating2Carrier surface and be made, Ru/SnO2The composition and its weight percent content of catalyst be：Ru 0.5 ~ 3.0%, SnO297.0~99.5%.The present invention catalyst can under relatively low reaction temperature by vinyl chloride complete oxidation be hydrogen chloride or chlorine, carbon dioxide and water, then absorbed with alkali lye, the qualified discharge of vinyl chloride waste gas is realized, the bigger many chlorine accessory substances of toxicity are not generated, it is to avoid secondary pollution.Cl species of the Deacon courses of reaction that the catalyst of the present invention can be catalyzed by Ru species by vinyl chloride in catalyst surface Dissociative are removed in time, catalyst is kept preferably activity, selectivity and stability.The Ru/SnO of the present invention2The preparation method of catalyst is infusion process, and preparation method is simple and easy to apply, it is easy to accomplish industrialization, catalyst activity is high, and stability is good.
Description
Technical field
The present invention relates to the Ru/SnO that burning is catalyzed for vinyl chloride for this2Catalyst and its preparation method and application, specifically
Ground is said, ruthenium trichloride is supported on to the SnO prepared with ammonia water precipitating using infusion process2Carrier surface and be made, belong to air
Contamination control field.
Background technology
Substantial amounts of low-level chlorinated ethene waste gas can be discharged in PVC Production Process, if be directly discharged in air
Meeting severe contamination environment simultaneously endangers public health.It is increasingly strict with various countries' environmental legislation and discharge standard, how effectively to locate
Managing such compound turns into the hot subject that various countries are studied.Catalytic combustion method has that operation temperature is low, purification efficiency is high and nothing
The advantages of secondary pollution, with wide prospects for commercial application, therefore, design has catalytic activity height and stability good with preparing
Catalyst it is most important.
In the catalytic combustion technology of vinyl chloride waste gas, conventional catalyst has perovskite type catalyst, and transition metal is multiple
Close oxide catalyst and loaded noble metal catalyst.Perovskite type catalyst Stability Analysis of Structures, heat endurance it is good and with compared with
High initial activity, such as document (Appl. Catal. B: Environ., 2013, 134-135:310-315) prepare
La0.8Ce0.2MnO3LaMnRu prepared by perovskite type catalyst and Chinese patent CN104888776A0.02O3+δCa-Ti ore type is catalyzed
Agent all shows preferable initial activity to the catalyst combustion reaction of vinyl chloride, but easily generate many chlorine accessory substances and catalyst because
Fluorine poisoning and inactivate.Transition metal composite oxide catalytic agent enjoys favor because of its cheap price and good activity, such as
Document (Chin. J. Catal., 2012,33:557-562) the CeO prepared2-MnOxCatalyst is 220oC realizes chloroethene
The complete burning of alkene, but easily generate many chlorine accessory substances and stability is also to be verified.Although loaded noble metal catalyst
With very high catalytic activity, but expensive, such as Degussa and Hoechst companies of Germany（Catal. Today,
1993, 17(1-2): 383-390）Joint development is used for the catalytic combustion technology that vinyl chloride waste gas purification is handled, and it is catalyzed
Burning bed is activated alumina and Pd-Pt/Al2O3Catalyst double-decker, bed inlet temperature is 350~380 DEG C, outlet temperature
580~680 DEG C of degree, but HCl, the Cl generated in course of reaction2And many chlorine accessory substances are readily adsorbed in catalyst surface, cause it
Inactivated because of fluorine poisoning.
Although catalyst prepared by above-mentioned document and patented technology respectively has its advantage, all have the following disadvantages：
Many chlorine accessory substances are easily generated, secondary pollution is caused；Catalyst active center easily inactivates because of fluorine poisoning, causes catalyst
Stability is bad.
The content of the invention
It is an object of the invention to provide a kind of Ru/SnO that burning is catalyzed for vinyl chloride2Catalyst and its preparation side
Method, to overcome the weak point that existing catalyst is present.
The Ru/SnO of the present invention that burning is catalyzed for vinyl chloride2The composition and its weight percent content of catalyst
For：
Ru 0.5 ~ 3.0%,
SnO2 97.0~99.5%。
The Ru/SnO of the present invention that burning is catalyzed for vinyl chloride2SnO in catalyst2Carrier, using ammonia precipitation process
Prepared by method, specifically include following steps：Stannic chloride is dissolved in deionized water, ammoniacal liquor is then added dropwise dropwise to pH value=8 ~ 11, after
Continuous stirring 1 ~ 6 hour, suction filtration, washing to neutrality dries gained precipitation 8 ~ 16 hours at 100 ~ 140 DEG C successively, 400 ~
1200 DEG C are calcined 2 ~ 6 hours in air atmosphere.
The Ru/SnO of the present invention that burning is catalyzed for vinyl chloride2Catalyst, is prepared using infusion process, is specifically included
Following steps：SnO prepared by ammonia water precipitating2Carrier is added in the ruthenium trichloride aqueous solution, is stirred in 40 ~ 80 DEG C of water-bath
Mix to drying, then dried 8 ~ 16 hours at 100 ~ 140 DEG C successively, is calcined 2 ~ 6 hours in air atmosphere at 300 ~ 500 DEG C.
Ru/SnO of the present invention2Catalyst is used in vinyl chloride catalyst combustion reaction, and its catalytic reaction condition is：Chlorine
The concentration of ethene is 1000 ~ 10000ppm, and reaction velocity is 15000 ~ 60000mL/ h gcat, reaction pressure be 0.1 ~
0.5MPa。
One of remarkable advantage of catalyst of the present invention is, the bigger many chlorine accessory substances of toxicity is not generated, it is to avoid secondary
Pollution, can under relatively low reaction temperature by vinyl chloride complete oxidation be hydrogen chloride or chlorine, carbon dioxide and water, then use alkali
Liquid is absorbed, and realizes the qualified discharge of vinyl chloride waste gas.
The remarkable advantage of the catalyst of the present invention two is, the Deacon courses of reaction being catalyzed by Ru species are by chloroethene
Alkene is removed in time in the Cl species of catalyst surface Dissociative, catalyst is kept preferably activity, selectivity and stability.
The remarkable advantage of the preparation method of the catalyst of the present invention is, is supported on ruthenium trichloride using infusion process and uses ammonia
SnO prepared by water sedimentation method2Carrier surface and be made, preparation method is simple and easy to apply, and catalyst activity is high, and stability is good.
Brief description of the drawings
Fig. 1 is SnO2The sintering temperature of carrier is to Ru/SnO2The influence of the catalytic activity of catalyst；
Fig. 2 is Ru load capacity to Ru/SnO2The influence of the catalytic activity of catalyst；
Fig. 3 is reaction velocity to Ru/SnO2The influence of the catalytic activity of catalyst；
Fig. 4 is vinyl chloride concentration to Ru/SnO2The influence of the catalytic activity of catalyst；
Fig. 5 is reaction pressure to Ru/SnO2The influence of the catalytic activity of catalyst；
Fig. 6 is 0.5%Ru/SnO2100 hours stability of catalyst.
Embodiment
With reference to specific embodiment, the present invention is described in detail, but is in no way intended to limit protection scope of the present invention.
Embodiment 1
SnO2The preparation of carrier：Weigh 14.02g SnCl4•5H2O, is dissolved in 150mL deionized waters, ammoniacal liquor is then slowly added dropwise
To pH value=8, continue to stir 3 hours, suction filtration, washing to neutrality, 120oC dries 12 hours, 550oC is calcined 4 hours, obtains SnO2
Carrier.
0.5%Ru/SnO2The preparation of catalyst：By 3.0g SnO2Carrier is added to 1.5g RuCl3In the aqueous solution（Ru's
Content is 1wt.%）, then 60oC stirred in water bath is to drying, 120oC dries 12 hours, 350oC is calcined 4 hours, is obtained
0.5%Ru/SnO2Catalyst.
Ru/SnO2The catalytic performance test condition of catalyst is：By 0.4 gram of Ru/SnO2Catalyst is placed in quartz ampoule fixed bed
It is that 1000ppm, reaction velocity are 15000mL/h g in vinyl chloride concentration using air as oxidant in reactorcatAnd reaction pressure
Power is progress vinyl chloride catalyst combustion reaction under conditions of 0.1MPa, and reaction end gas is detected with capillary gaschromatography instrument.
Embodiment 2
Change SnO2The sintering temperature of carrier is respectively 400oC、600oC、800oC、1000oC and 1200oC, SnO2Carrier other
Preparation process is same as Example 1.0.5%Ru/SnO2The preparation process and catalytic performance test condition of catalyst and embodiment 1
It is identical.
SnO2The sintering temperature of carrier is to Ru/SnO2The influence of the catalytic activity of catalyst is as shown in Figure 1.
Embodiment 3
The load capacity for changing Ru is respectively 1%, 2% and 3%, Ru/SnO2Other preparation process of catalyst are same as Example 1.
SnO2The preparation process and Ru/SnO of carrier2The catalytic performance test condition of catalyst is same as Example 1.
Ru load capacity is to Ru/SnO2The influence of the catalytic activity of catalyst is as shown in Figure 2.
Embodiment 4
It is respectively 30000mL/h g to change reaction velocitycat、45000mL/h•gcatWith 60000mL/h gcat, SnO2The system of carrier
Standby process, 0.5%Ru/SnO2The preparation process of catalyst and other catalytic performance test conditions are same as Example 1.
Reaction velocity is to Ru/SnO2The influence of the catalytic activity of catalyst is as shown in Figure 3.
Embodiment 5
It is respectively 3000ppm, 5000ppm and 10000ppm, SnO to change vinyl chloride concentration2The preparation process of carrier, 0.5%Ru/
SnO2The preparation process of catalyst and other catalytic performance test conditions are same as Example 1.
Vinyl chloride concentration is to Ru/SnO2The influence of the catalytic activity of catalyst is as shown in Figure 4.
Embodiment 6
It is respectively 0.2MPa, 0.3MPa and 0.5MPa, SnO to change reaction pressure2The preparation process of carrier, 0.5%Ru/SnO2Urge
The preparation process of agent and other catalytic performance test conditions are same as Example 1.
Reaction pressure is to Ru/SnO2The influence of the catalytic activity of catalyst is as shown in Figure 5.
Embodiment 7
0.5%Ru/SnO prepared by 0.4 gram of embodiment 12Catalyst is placed in quartz ampoule fixed bed reactors, using air as oxygen
Agent, is that 1000ppm, reaction velocity are 15000mL/h g in vinyl chloride concentrationcat, reaction pressure be 0.1MPa and reaction temperature
For 250oThe vinyl chloride catalyst combustion reaction of progress 100 hours, 0.5%Ru/SnO is investigated with this under conditions of C2The stabilization of catalyst
Property, experimental result is as shown in Figure 6.
Claims (4)
1. the Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst, it is characterised in that the composition and its weight hundred of the catalyst
Divide and be than content：
Ru 0.5 ~ 3.0%,
SnO2 97.0~99.5%。
2. it is used for the Ru/SnO that vinyl chloride is catalyzed burning described in claim 12Catalyst, it is characterised in that described SnO2Carry
Body is prepared using ammonia water precipitating, specifically includes following steps：Stannic chloride is dissolved in deionized water, ammoniacal liquor is then added dropwise dropwise
To pH value=8 ~ 11, continue to stir 1 ~ 6 hour, suction filtration, washing to neutrality, gained precipitation is dried 8 ~ 16 at 100 ~ 140 DEG C successively
Hour, it is calcined 2 ~ 6 hours in air atmosphere at 400 ~ 1200 DEG C.
3. it is used for the Ru/SnO that vinyl chloride is catalyzed burning described in preparation claim 1 and claim 22The method of catalyst, its
It is characterised by, the preparation method is infusion process, specifically includes following steps：SnO prepared by ammonia water precipitating2Carrier is added to
In the ruthenium trichloride aqueous solution, in 40 ~ 80 DEG C of stirred in water bath to drying, then dried 8 ~ 16 hours at 100 ~ 140 DEG C successively,
It is calcined 2 ~ 6 hours in air atmosphere at 300 ~ 500 DEG C.
4. it is used for the Ru/SnO that vinyl chloride is catalyzed burning described in claim 12The application of catalyst, it is characterised in that it is catalyzed
Reaction condition is：The concentration of vinyl chloride is 1000 ~ 10000ppm, and reaction velocity is 15000 ~ 60000mL/h gcat, reaction pressure
For 0.1 ~ 0.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710446994.3A CN107233882A (en) | 2017-06-14 | 2017-06-14 | The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application |
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| CN201710446994.3A CN107233882A (en) | 2017-06-14 | 2017-06-14 | The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application |
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| CN201710446994.3A Pending CN107233882A (en) | 2017-06-14 | 2017-06-14 | The Ru/SnO of burning is catalyzed for vinyl chloride2Catalyst and its preparation method and application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395730A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for vinyl chloride low-temperature catalytic burning ruthenium cerium codope tin-based catalyst and products thereof and application |
| CN112547059A (en) * | 2020-09-07 | 2021-03-26 | 北京工业大学 | Ru/3DOM SnO with good stability2Preparation method and application of catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58180939A (en) * | 1982-04-17 | 1983-10-22 | Fuigaro Giken Kk | Element for detecting combustion state |
| WO1995031675A1 (en) * | 1994-05-11 | 1995-11-23 | Johnson Matthey Public Limited Company | Catalytic combustion |
| CN102353065A (en) * | 2011-06-28 | 2012-02-15 | 华东理工大学 | Method for eliminating chlorinated aliphatic hydrocarbons through low temperature catalytic combustion |
| CN104888776A (en) * | 2015-05-27 | 2015-09-09 | 华东理工大学 | Perovskite type catalyst for chloroethylene catalytic elimination and preparation method of perovskite type catalyst |
-
2017
- 2017-06-14 CN CN201710446994.3A patent/CN107233882A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58180939A (en) * | 1982-04-17 | 1983-10-22 | Fuigaro Giken Kk | Element for detecting combustion state |
| WO1995031675A1 (en) * | 1994-05-11 | 1995-11-23 | Johnson Matthey Public Limited Company | Catalytic combustion |
| CN102353065A (en) * | 2011-06-28 | 2012-02-15 | 华东理工大学 | Method for eliminating chlorinated aliphatic hydrocarbons through low temperature catalytic combustion |
| CN104888776A (en) * | 2015-05-27 | 2015-09-09 | 华东理工大学 | Perovskite type catalyst for chloroethylene catalytic elimination and preparation method of perovskite type catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 俞静: "贵金属Ru改性SnO2催化剂的催化化学研究", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109395730A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for vinyl chloride low-temperature catalytic burning ruthenium cerium codope tin-based catalyst and products thereof and application |
| CN109395730B (en) * | 2018-11-15 | 2021-04-13 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ruthenium and cerium co-doped tin-based catalyst for low-temperature catalytic combustion of vinyl chloride, product and application thereof |
| CN112547059A (en) * | 2020-09-07 | 2021-03-26 | 北京工业大学 | Ru/3DOM SnO with good stability2Preparation method and application of catalyst |
| CN112547059B (en) * | 2020-09-07 | 2024-01-26 | 北京工业大学 | Ru/3DOM SnO with good stability 2 Preparation method and application of catalyst |
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Application publication date: 20171010 |